JP6842235B2 - Method of forming a collector electrode protective film for dye-sensitive solar cells - Google Patents

Description

The present invention relates to a dye-sensitive solar cell collector electrode protective film and a method for forming the same, and a dye-sensitive solar cell including the same. More specifically, the superhydrophobic reduced graphene oxide is used as the first barrier layer as the collector electrode protective film. By applying it, the metal surface of the collector electrode can be protected from moisture, electrolytes, air, etc., corrosion can be prevented, and the current collection efficiency can be improved. Regarding dye-sensitive solar cells including.

When the size of a solar cell increases, the current collecting efficiency decreases due to the resistance of the transparent conductive layer. To compensate for this, metal electrodes are generally further inserted. However, in the inserted metal electrode, the phenomenon that the electrode is corroded by the electrolyte, particularly the iodine-based electrolyte, frequently occurs.
Therefore, an example in which a glass frit, a UV curable or a thermosetting polymer resin film is applied as a new electrode protective layer has been reported. However, although glass frit is a glass material and is an excellent protective material, it has not been used much recently because it cannot completely protect the collector electrode within the allowable temperature range of the solar cell manufacturing process. In particular, there is a high possibility that cracks or cracks will occur when pressure is applied or when vibration or impact is transmitted from the outside, so that there is a drawback that it is difficult to use as a member for preventing corrosion by an electrolyte.
Epoxy resins are also classified as thermosetting resins that have an epoxy group, and when used, they are used together with a curing agent. Once such an epoxy resin is heated and cured and molded, its form does not change even if heat is further applied, and it has excellent heat resistance and adhesiveness, so that it is generally widely used as an adhesive material. However, it is not appropriate to use it as a barrier layer because the environmental hormones produced when using epoxy resin may adversely affect the human body as a disruptor, and it completely prevents corrosion by iodine-based electrolytes. It is also a difficult material.

Further, in the UV curing agent, the photopolymerization reaction is started when the photoinitiator contained in a trace amount in the ultraviolet curable resin receives ultraviolet rays, and the monomer (monomer) or oligomer (oligomer) which is the main component of the resin is started. Is used in various fields as a material that instantly becomes a polymer and cures. However, there is a large difference in curing speed due to the difference in the thickness of the UV curing agent, which makes it difficult to cure non-planar parts such as corners and uneven parts. In addition, iodine-based electrolytes are used as in thermosetting materials. It is a material that is difficult to prevent completely.
Graphene, a material that has been in the limelight as a new material in recent years, is a carbon material with a honeycomb-like hexagonal lattice structure made of carbon atoms, and due to its unique properties, it is used in various fields. Research is progressing. Methods for producing graphene include a method of directly depositing graphene on a substrate such as copper foil, a mechanical peeling method, and a chemical peeling method. Among these, redox graphene produced by a chemical stripping method using an oxidation-reduction reaction is a carbon nanomaterial consisting of a single layer to several tens of layers, including high transmittance, organic solvent, heat, and light. and it has excellent characteristics in durability against such hydrogen sulfide (H 2 _S).

Patent Document 1 describes a transparent electrode including a base material, a first electrode layer formed on the base material, and a graphene oxide layer formed above and / or a lower part of the first electrode layer, and an electronic material containing the same. It is disclosed.
Further, Patent Document 2 discloses an electronic material having a transparent electrode including a base material, a first electrode layer on the base material, and a graphene oxide layer formed above and / or below the first electrode layer. There is.
Further, Patent Document 3 discloses a metal flexible dye-sensitive solar cell characterized in that the protective film and the transparent carbon-based thin film are carbon nanotubes or graphene thin films.
However, as described above, graphene oxide (hereinafter abbreviated as GO) formed on the transparent electrode has excellent durability against organic solvents, heat, light, gas, etc., but is the most important in the present invention. No consideration is given to the problem of corrosion caused by iodine-based electrolytes.
Under the above circumstances, it was necessary to study a new material as an electrode protective layer that can prevent electrode corrosion and improve current collection efficiency.

Republic of Korea Patent Publication No. 2013-0127781 Republic of Korea Patent Publication No. 2014-0071314 Republic of Korea Patent Registration No. 10-1192981

The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to make the metal surface of the collector electrode as a collector electrode protective film not only water or air (oxygen) but also an iodine system. It is an object of the present invention to provide a dye-sensitive electrode collecting electrode protective film for a dye-sensitive solar cell which also protects from an electrolyte and prevents corrosion, and a method for forming the same.
Still another object of the present invention is to provide a dye-sensitive solar cell including the above-mentioned collector electrode protective film.

The dye-sensitive solar cell collector electrode protective film of the present invention made to achieve the above object is a transparent electrode layer in which a plurality of metal electrodes are separated and arranged on a transparent electrode substrate, and an electrode layer is formed. It is characterized by including a first barrier layer partially formed on the entire surface of the electrode substrate or only on the electrode layer, and the first barrier layer is reduced graphene oxide (hereinafter abbreviated as rGO). To do.

In the method for forming the electrode collecting electrode protective film for a dye-sensitive solar cell of the present invention, a step of forming an electrode layer by arranging a plurality of electrodes at predetermined intervals on a transparent electrode substrate at a predetermined interval and forming an electrode layer are formed. The step of forming the first barrier layer includes the step of partially forming the first barrier layer on the entire surface of the transparent electrode substrate or only on the electrode layer, and the step of forming the first barrier layer is performed in the step of forming the reduced graphene oxide layer. It is a feature.

Further, the dye-sensitive solar cell of the present invention is characterized by including the above-mentioned collector electrode protective film.

According to the present invention, by applying superhydrophobic reduced graphene oxide as a first barrier layer as a collector electrode protective film, the metal surface of the collector electrode is protected from iodine-based electrolyte and moisture or air (oxygen) and corroded. Can be prevented and the collection efficiency can be improved.
Further, by further coating the reduced graphene oxide with a polymer film or a silicon film to form a double-structured collector electrode protective film, corrosion of the collector electrode can be prevented.

It is a process drawing which showed the method of forming the collecting electrode protective film by Example 1 of this invention. It is sectional drawing of the collecting electrode protective film by Example 1 of this invention. It is a process drawing which showed the method of forming the collecting electrode protective film by Example 2 of this invention. It is sectional drawing of the collecting electrode protective film by Example 2 of this invention. It is a process drawing which showed the method of forming the collecting electrode protective film by Example 3 of this invention. It is sectional drawing of the collecting electrode protective film by Example 3 of this invention. It is a process drawing which showed the method of forming the collecting electrode protective film by the comparative example 1 of this invention. It is sectional drawing of the collecting electrode protective film by the comparative example 1 of this invention. It is a chart which shows the X-ray photoelectron spectroscopy (XPS) measurement result of rGO and GO by Example 1 and Comparative Example 1 of this invention. It is a chart which shows the X-ray photoelectron spectroscopy (XPS) measurement result of rGO by Example 1 of this invention. It is a chart which shows the X-ray photoelectron spectroscopy (XPS) measurement result of GO by the comparative example 1 of this invention. It is a scanning electron microscope (SEM) photograph of a collecting electrode protective film according to Example 1 of this invention, (a) is an image of magnification × 2,000, (b) is an image of magnification × 15,000. It is a photograph of a dye-sensitive solar cell manufactured from the collector electrode protective film according to Example 1 of the present invention, (a) is an image of the front surface where GO is formed on a silver collector electrode, and (b) is an image of the back surface. Shown. It is a photograph which shows the corrosiveness evaluation result of the dye sensitive solar cell produced from the electrode collector protective film according to Example 1 of this invention, (a) is photograph before the electrolyte impregnation, (b) is the photograph after impregnation with the electrolyte for 500 hours. Is. It is a photograph which shows the corrosiveness evaluation result of the dye sensitive solar cell manufactured from the electrode collector protective film by the comparative example 1 of this invention, (a) is a photograph before impregnation of an electrolyte, (b) is a photograph after impregnation with an electrolyte for 150 hours. Is. It is a photograph which shows the corrosiveness evaluation result of the dye sensitive solar cell manufactured from the electrode collector protective film by the comparative example 2 of this invention, (a) is a state that Ag current collection barrier layer was formed before electrolyte impregnation, (a). In b), the electrolyte permeated the barrier layer 24 hours after the impregnation of the electrolyte, and the collector electrode was corroded and the electrode was cut.

Hereinafter, the present invention will be described in more detail based on one example.
The electrode collecting electrode protective film for a dye-sensitive solar cell of the present invention has an electrode layer in which a plurality of metal electrodes are separated and arranged on a transparent electrode substrate, and the entire surface of the transparent electrode substrate on which the electrode layers are formed or on the electrode layer. It comprises a first barrier layer, which is only partially formed, characterized in that the first barrier layer is reduced graphene oxide (RGO).
According to a preferred embodiment of the present invention, the transparent electrode is a group consisting of fluorine-doped tin oxide (hereinafter abbreviated as FTO), indium-doped tin oxide (hereinafter abbreviated as ITO), graphene, silver nanowires and a conductive polymer. You can use the type selected from.

According to a preferred embodiment of the present invention, the metal electrodes are silver (Ag), copper (Cu), aluminum (Al), gold (Au), platinum (Pt), palladium (Pd), iron (Fe), zinc. (Zn), titanium (Ti), chromium (Cr), it can be used nickel (Ni) and cobalt (C o) 1 or more selected from the group consisting of.
According to a preferred embodiment of the present invention, the first barrier layer is formed on the entire surface of the transparent electrode substrate on which the electrode layer is formed or only partially on the electrode layer. In particular, when the barrier layer is partially formed only on the electrode layer, there is an advantage that it is advantageous to ensure the transparency of the dye-sensitive solar cell.
According to a preferred embodiment of the present invention, the first barrier layer can use reduced graphene oxide (rGO). The reduced graphene oxide, unlike graphene oxide, has the property of having superhydrophobic properties while having conductivity. In addition, it has the characteristic that it can be mass-produced while having characteristics similar to those of graphene produced by the direct vapor deposition method. Such reduced graphene oxide can reduce graphene oxide to form reduced graphene oxide having superhydrophobic properties. The superhydrophobic properties of the reduced graphene oxide can protect the electrode layer by blocking the electrode collector from being corroded by the iodine-based electrolyte.

According to a preferred embodiment of the present invention, the first barrier layer preferably has a thickness of 0.01 to 100 μm. If the thickness of the first barrier layer is less than 0.01 μm, the electrolyte permeation cannot be effectively prevented, and the collector electrode may be corroded. If the thickness of the first barrier layer is thicker than 100 μm, the adhesive force with the substrate is inferior, and the first barrier layer may be peeled off from the substrate, making it impossible to perform the barrier function.
According to the present invention, it is preferable to further include a first barrier layer or a second barrier layer formed on the entire surface of the transparent electrode substrate on which the first barrier layer is partially formed.
According to a preferred embodiment of the present invention, the second barrier layer is preferably a polymer film or a silicon film of polyvinyl alcohol (PVA) or a silane compound. The second barrier layer serves to protect the collector electrode from corrosion by eliminating the possibility of electrolyte penetration between the bulk structures of the first barrier layer forming material, rGO. The second barrier layer can be omitted depending on the requirements.
According to a preferred embodiment of the present invention, the second barrier layer preferably has a thickness of 0.1 to 200 μm. If the thickness of the second barrier layer is thinner than 0.1 μm, the barrier function may not be sufficiently exhibited. Further, if the thickness of the second barrier layer is thicker than 200 μm, the distance between the upper and lower plates of the solar cell becomes large, which is disadvantageous in terms of performance and may deteriorate the performance of the final product.

On the other hand, in the method for forming the electrode collecting electrode protective film for a dye-sensitive solar cell of the present invention, a step of forming an electrode layer by arranging a plurality of electrodes separated from each other at predetermined intervals on a transparent electrode substrate and forming an electrode layer. The step of forming the first barrier layer includes the step of partially forming the first barrier layer on the entire surface or only on the electrode layer of the transparent electrode substrate, and the step of forming the first barrier layer is performed in the step of forming the reduced graphene oxide layer. It is characterized by that.
According to a preferred embodiment of the present invention, the first barrier layer is selected from a group of construction methods consisting of spray coating, roll coating, slot die coating, bar coating, spin coating, inkjet coating and dip coating. It can be formed by one method, but it is not limited to this. Preferably, the first barrier layer is formed by a spray coating method. When the first barrier layer is partially formed only on the electrode layer, it is preferable to use a mask sheet to coat unnecessary portions so that the first barrier layer is not formed.

According to a preferred embodiment of the present invention, the step of forming the first barrier layer can also be carried out by a step of coating with a reduced graphene oxide solution. Specifically, it is preferable that the reduced graphene oxide solution is partially coated on the entire surface of the transparent electrode substrate on which the electrode layer is formed or only on the electrode layer to form the first barrier layer.
The step of forming the first barrier layer consists of a step of coating the graphene oxide solution and a subsequent step of reducing the coated graphene oxide to form the reduced graphene oxide. Here, the graphene oxide solution can be produced by a direct synthesis method using graphene, a mechanical stripping method, a chemical stripping method, or the like. Preferably, it is a chemical stripping method for producing graphene in which a large number of graphenes are laminated by a chemical treatment such as an acid treatment. In the acid-treated graphite, a part of the graphene surface has a hydroxyl group (-OH) or a hydroxycarbonyl group (-COOH), and by putting this in water or an organic solvent and dispersing it, graphene oxide (Graphene) is dispersed. Oxide: GO) solution is produced.
The graphene oxide solution is preferably partially coated on the entire surface of the transparent electrode substrate on which the electrode layer is formed or only on the electrode layer.
The step of reducing graphene oxide is to _{react in an atmosphere of argon (Ar) gas containing 4% hydrogen (H 2} ) at a temperature of 200 to 500 ° C. for 1 to 10 hours. Specifically, the surface coated with the graphene oxide solution is reduced in a high vacuum furnace at a high temperature of 200 to 500 ° C. to form a first barrier layer of the reduced graphene oxide. be able to. If the temperature of the reduction reaction is lower than 200 ° C., a part of the hydroxycarbonyl group (-COOH) and the hydroxyl group (-OH) remains, so that the superhydrophobicity characteristic of rGO may not be exhibited. If the temperature of the reduction reaction is higher than 500 ° C., heat equal to or higher than the temperature required for the solar cell manufacturing process is applied, which may deteriorate the performance of the solar cell.

According to a preferred embodiment of the present invention, the solid content of the graphene oxide solution or the reduced graphene oxide solution is preferably 0.01 to 50 mg / ml. If the solid content is less than 0.01 mg / ml, the collector electrode may not be completely covered, while if the solid content is more than 50 mg / ml, the dispersibility of the solution deteriorates. Uniform coating becomes difficult, and the performance of the finished solar cell may deteriorate.
According to a preferred embodiment of the present invention, the first barrier layer preferably has a thickness of 0.01 to 100 μm.
According to a preferred embodiment of the present invention, it is preferable to further include a step of forming the second barrier layer on the entire surface of the transparent electrode substrate on which the first barrier layer or the first barrier layer is partially formed.

According to a preferred embodiment of the present invention, the second barrier layer is preferably a polymer film or a silicon film of polyvinyl alcohol (PVA) or a silane compound. Specifically, in the case of polyvinyl alcohol, it is prepared by mixing 0.1 to 10% by weight of polyvinyl alcohol with one or more solvents selected from the group consisting of water, ethanol, methanol, acetone, isopropyl alcohol and butanol. The polyvinyl alcohol solution can be coated to form a second barrier layer.
According to a preferred embodiment of the present invention, the second barrier layer preferably has a thickness of 0.1 to 200 μm.

On the other hand, the present invention provides a dye-sensitive solar cell including a collector electrode protective film.
By applying superhydrophobic reduced graphene oxide as the electrode collector protective film according to the present invention, the metal surface of the collector electrode is protected from iodine-based electrolytes and moisture or air (oxygen) to prevent corrosion and collect electricity. Efficiency can be improved. Further, by further coating the reduced graphene oxide with a polymer film or a silicon film to form a double-structured collector electrode protective film, corrosion of the collector electrode can be prevented.
Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to the following Examples.

[Example 1]
A silver (Ag) paste is coated on glass coated with fluorine-doped tin oxide (FTO), which is a substance for transparent electrodes constituting a dye-sensitive solar cell, and then heat-treated at 500 ° C. for 30 minutes to produce a silver (Ag) electrode. Was formed. Then, 5 mg / mL of the GO solution was coated by a spray coating method, and then the coated GO was reduced at 300 ° C. for 5 hours while flowing an argon (Ar) gas mixture containing _{4% hydrogen (H 2) to obtain rGO.} A first barrier layer was formed. The thickness of the formed first barrier layer was 0.5 μm. Then, a solution prepared by dissolving 5% by weight of PVA in ethanol was coated on the first barrier layer by a spray method to form a second barrier layer. At this time, the thickness of the second barrier layer was 10 μm.
FIG. 1 is a process diagram showing a method for forming a collector electrode protective film according to Example 1 of the present invention, and FIG. 2 is a cross-sectional view of the collector electrode protective film according to Example 1 of the present invention. As shown in FIGS. 1 and 2, an electrode layer was formed so that Ag electrodes were separated and arranged on the glass coated with FTO. A first barrier layer coated with rGO is formed by first coating GO on a glass substrate containing an Ag electrode and then reducing this, and then PVA is secondarily coated on the first barrier layer coated with rGO. A second barrier layer was formed to form a collecting electrode protective film.

[Example 2]
An Ag paste was coated on glass coated with FTO, which is a substance for a transparent electrode constituting a dye-sensitive solar cell, and then heat-treated at 500 ° C. for 30 minutes to form an Ag electrode. After attaching the mask sheet so that only the Ag electrode could be coated, 5 mg / mL of the GO solution was coated on the mask sheet by the spray coating method. By removing the mask sheet and _{reducing the partially coated GO at 300 ° C. for 5 hours while flowing a hydrogen (H 2} ) -containing argon (Ar) gas mixture, rGO was coated only on the Ag electrode. A first barrier layer was formed. The thickness of the formed first barrier layer was 0.5 μm. Then, a solution prepared by dissolving 5% by weight of PVA in ethanol was coated on the entire surface of the first barrier layer and the FTO layer by a spray method to form a second barrier layer. At this time, the thickness of the second barrier layer was 10 μm.
FIG. 3 is a process diagram showing a method for forming the collector electrode protective film according to the second embodiment of the present invention, and FIG. 4 is a cross-sectional view of the collector electrode protective film according to the second embodiment of the present invention. As shown in FIGS. 3 and 4, the electrode layer was formed so that the Ag electrodes were separated and arranged on the glass coated with FTO. A mask sheet is used to partially primary coat GO only on the electrode layer, and then this is reduced to form a first barrier layer coated with rGO, which is then secondarily coated with PVA. Then, a second barrier layer was formed to form a collecting electrode protective film.

[Example 3]
An Ag paste was coated on glass coated with FTO, which is a substance for a transparent electrode constituting a dye-sensitive solar cell, and then heat-treated at 500 ° C. for 30 minutes to form an Ag electrode. Then, a 5 mg / mL rGO solution was coated by a spray coating method and then dried at 300 ° C. for 1 hour to form a first barrier layer. The thickness of the formed first barrier layer was 0.5 μm. Then, a solution prepared by dissolving 5% by weight of PVA in ethanol was coated on the first barrier layer by a spray method to form a second barrier layer. At this time, the thickness of the second barrier layer was 20 μm.
FIG. 5 is a process diagram showing a method for forming the collector electrode protective film according to the third embodiment of the present invention, and FIG. 6 is a cross-sectional view of the collector electrode protective film according to the third embodiment of the present invention. As shown in FIGS. 5 and 6, the electrode layer was formed so that the Ag electrodes were separated and arranged on the glass coated with FTO. Further, rGO was primarily coated to form a first barrier layer, which was then secondarily coated with PVA to form a second barrier layer to form a collecting electrode protective film.

[Example 4]
After dispersing GO in 5 mg / mL water, 1 ml of hydrazine hydrate was added, and the mixture was reacted at 80 ° C. for 3 hours. Then, the solvent was removed, washed with ethanol, and dried for 15 hours to obtain rGO. The obtained rGO was dispersed in a DMF solvent. At this time, in order to improve the solubility of the solution, 5 mL of aqueous ammonia was added, reacted for 2 hours, and then the aqueous ammonia was removed. Then, the produced rGO 5 mg / mL was directly coated on the glass coated with FTO, which is a substance for a transparent electrode constituting a dye-sensitive solar cell, to form a first barrier layer. The thickness of the formed first barrier layer was 0.5 μm. Then, a solution prepared by dissolving 5% by weight of PVA in ethanol was coated on the first barrier layer by a spray method to form a second barrier layer. At this time, the thickness of the second barrier layer was 20 μm.

[Comparative Example 1]
An Ag paste was coated on glass coated with FTO, which is a substance for a transparent electrode constituting a dye-sensitive solar cell, and then heat-treated at 500 ° C. for 30 minutes to form an Ag electrode. Then, 5 mg / mL of GO solution was coated by a spray coating method, and then dried at 300 ° C. for 1 hour to form a first barrier layer. The thickness of the formed first barrier layer was 0.5 μm. Then, a solution of PVA dissolved in 5% by weight ethanol was coated on the first barrier layer by a spray method to form a second barrier layer. At this time, the thickness of the second barrier layer was 20 μm.
FIG. 7 is a process diagram showing a method for forming the collector electrode protective film according to Comparative Example 1 of the present invention, and FIG. 8 is a cross-sectional view of the collector electrode protective film according to Comparative Example 1 of the present invention. As shown in FIGS. 7 and 8, the electrode layer was formed so that the Ag electrodes were separated and arranged on the glass coated with FTO. Further, GO was primarily coated to form a first barrier layer, which was then secondarily coated with PVA to form a second barrier layer to form a collector electrode protective film.

[Comparative Example 2]
A silver (Ag) paste was coated on glass coated with FTO, which is a substance for a transparent electrode constituting a dye-sensitive solar cell, and then heat-treated at 500 ° C. for 30 minutes to form a silver (Ag) electrode. Then, an epoxy-based UV curing agent was coated by a screen printing method, dried at 80 ° C. for 30 minutes, and cured by irradiation with ultraviolet rays to form a barrier layer. The thickness of the formed barrier layer was 30 μm.

[Experimental Example 1]
In order to confirm the coating substance of the first barrier layer of the collector electrode protective film produced in Example 1 and Comparative Example 1, X-ray photoelectron spectroscopy (XPS) measurement was carried out, and the results are shown in FIGS. 9 to 11. It was.
FIG. 9 is a chart showing XPS measurement results of rGO and GO according to Example 1 and Comparative Example 1 of the present invention. Further, FIG. 10 is a chart showing the XPS measurement result of rGO according to Example 1 of the present invention, and FIG. 11 is a chart showing the XPS measurement result of GO according to Comparative Example 1 of the present invention.
As shown in the charts of FIGS. 9, 10 and 11, in Example 1 and Comparative Example 1, the C of XPS measurement showed that the coating layers of GO and rGO, which are the first barrier layers, were surely formed, respectively. It could be confirmed from the peaks such as −O and C = O.

FIG. 12 is a scanning electron microscope (SEM) photograph of the electrode collecting electrode protective film according to the first embodiment of the present invention. As shown in FIGS. 12 (a) and 12 (b), it was observed that the GO film was surely formed on the silver (Ag) electrode, and it was confirmed that the thickness was 0.5 μm.
FIG. 13 is a photograph showing a dye-sensitive solar cell manufactured from the electrode collecting electrode protective film according to the first embodiment of the present invention. FIG. 13A is an image of the front surface in which the GO is formed on the silver collector electrode, and FIG. 13B is an image of the back surface. Since there is no change in the hue of the silver collector electrode, the silver collector is formed when the GO is formed. It was confirmed that the electrodes were not damaged.

[Experimental Example 2]
After impregnating the iodine-based electrolyte with the dye-sensitive solar cells produced from the electrode collecting electrode protective films produced in Examples 1 and Comparative Examples 1 and 2 for each predetermined time, the surface of the dye-sensitive solar cells was visually confirmed. The results are shown in FIGS. 14, 15, and 16.
FIG. 14 is a photograph showing the corrosiveness evaluation result of the dye-sensitive solar cell produced from the electrode collecting electrode protective film according to Example 1 of the present invention. FIG. 14 (a) is before electrolyte impregnation, and FIG. 14 (b) is 500 hours. It is a photograph which shows the dye-sensitive solar cell after impregnating with an electrolyte. After 500 hours in (b) of FIG. 14, a portion (white portion) on which the collector electrode protective film was formed was confirmed, but the white portion was maintained in a stable state as compared with (a). It was confirmed that there were no traces of corrosion.

FIG. 15 is a photograph showing the corrosiveness evaluation result of the dye-sensitive solar cell produced from the electrode collecting electrode protective film according to Comparative Example 1 of the present invention. FIG. 15 (a) is before electrolyte impregnation, and FIG. 15 (b) is 150 hours. It is a photograph which shows the dye-sensitive solar cell after impregnating with an electrolyte. In FIG. 15 (b), it was confirmed that the portion (white portion) on which the collector electrode protective film was formed was corroded as compared with (a) for the first time in 150 hours after impregnation with the electrolyte.
FIG. 16 is a photograph showing the corrosiveness evaluation result of the dye-sensitive solar cell produced from the electrode collector protective film according to Comparative Example 2 of the present invention, and FIG. 16A shows an Ag current collector barrier layer formed before the electrolyte impregnation. The state was shown in (b), in which the electrolyte permeated the barrier layer 24 hours after the impregnation of the electrolyte, the collector electrode was corroded, and the electrode was cut.

From the above, by applying reduced graphene oxide having superhydrophobicity as the electrode collector protective film according to the present invention, the metal surface of the collector electrode is protected from iodine-based electrolyte and moisture or air (oxygen) and corroded. It was confirmed that this can be prevented and the collection efficiency can be improved.

FTO: Fluorine-topped tin oxide
Glass: Glass GO: Graphene oxide
ITO: Indium-doped tin oxide
PVA: Polyvinyl alcohol
rGO: Reduced graphene oxide
SEM: Scanning Electron Microscope
XPS: X-ray Photoelectron Spectroscopy

Claims (7)

Step to form an electrode layer and arranged at a distance a plurality of electrodes at predetermined intervals on the transparent electrode substrate, and only partly on the entire surface or the electrode layer of the said transparent electrode substrate with an electrode layer is formed Including the stage of forming the first barrier layer,
The step of forming the first barrier layer is carried out in a step of coating the graphene oxide solution and a step of reducing the coated graphene oxide to form the reduced graphene oxide.
A method for forming a dye-sensitive solar cell collector electrode protective film, wherein the step of reducing the coated graphene oxide is carried out at a temperature of 200 to 500 ° C. for 1 to 10 hours. Step to form an electrode layer and arranged at a distance a plurality of electrodes at predetermined intervals on the transparent electrode substrate, and only partly on the entire surface or the electrode layer of the said transparent electrode substrate with an electrode layer is formed Including the stage of forming the first barrier layer,
A method for forming a dye-sensitive solar cell collector electrode protective film, wherein the step of forming the first barrier layer is performed in a step of coating a reduced graphene oxide solution and then drying. The formation of the electrode collecting electrode protective film for a dye-sensitive solar cell according to claim 1 or 2 , wherein the solid content of the graphene oxide solution or the reduced graphene oxide solution is 0.01 to 50 mg / ml. Method. The method for forming a dye-sensitive solar cell collecting electrode protective film according to claim 1 or 2 , wherein the first barrier layer has a thickness of 0.01 to 100 μm. According to claim 1 or 2, wherein the first barrier layer or said first barrier layer further comprises a step, forming a second barrier layer on the partially formed transparent electrode substrate on the entire surface A method for forming a collector electrode protective film for a dye-sensitive solar cell. The method for forming a dye-sensitive solar cell collector electrode protective film according to claim 5 , wherein the second barrier layer is a polymer film or a silicon film of polyvinyl alcohol (PVA) or a silane compound. The method for forming a dye-sensitive solar cell collector electrode protective film according to claim 5 , wherein the second barrier layer has a thickness of 0.1 to 200 μm.

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